Aqueous adhesive system, method for the production and use thereof

ABSTRACT

An aqueous adhesive system consisting of two separate components, A and B. Component A is an aqueous dispersion of polymer containing at least one olefinically unsaturated double bond and Component B consists of a dispersion of a drying agent in an oil phase liquid. The adhesive produced by this system is useful for bonding material made of wood, cork, metal, plastic, stone and concrete.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a national stage application under 35 USC 371 ofinternational application PCT/EP01/08765 filed on Jul. 28, 2001, theinternational application not being published in English. Thisapplication also claims priority under 35 USC 119 to DE 100 38 934.1file on Aug. 9, 2000.

BACKGROUND OF THE INVENTION

This invention relates to an adhesive system of at least two separatecomponents A and B, the adhesive system comprising

-   a) as component A an aqueous dispersion of a polymer obtainable by    polyaddition or by polymerization of a monomer containing at least    one olefinically unsaturated double bond or a mixture of two or more    such monomers or an aqueous dispersion of a mixture of two or more    such polymers and-   b) as component B a dispersion of a drying agent in an oil phase    liquid at 23° C., the oil phase containing at least 0.1% by weight    of a compound liquid at 23° C. which is soluble in the oil phase and    which contains at least one covalent single, double or triple bond    between a carbon atom and a hetero atom or a mixture of two or more    such compounds,    to a process for the production of an adhesive of components A and B    and to the use of component B for the production of binders or    adhesives, coating compositions and sealants.

Water-based adhesive dispersions are used in many branches of industryfor bonding substrates to one another. The use of water-based adhesivedispersions is particularly advantageous when, on the one hand, nosolvent-containing vapors are intended to enter the environment duringbonding while, on the other hand, the water present in the water-basedadhesive dispersion is intended to be able to evaporate withoutdifficulty. However, the use of water-based adhesive dispersions isproblematical in particular when either the bonding conditions make itdifficult or even impossible for the water to evaporate or the substrateto be bonded is sensitive to water, so that the use of a water-basedadhesive dispersion causes damage to the substrate. In addition,water-based adhesives are also not generally suitable for use when thebond is likely to be exposed at least temporarily to an environment ofextremely high atmospheric humidity, but is not expected to lose any ofits strength under such conditions, or when the bond is exposed eventemporarily or permanently to direct contact with water.

Accordingly, water-free adhesives have hitherto been used in thelast-mentioned cases, developing their adhesive strength either throughthe evaporation of a readily volatile solvent or by reaction of twointer-reactive components. Adhesives of the first type are attended bythe disadvantage that solvents are emitted into the environment which isnot desirable where the adhesives are used indoors in view of thepossible health risk posed by the solvents and the noxious odor problemassociated with solvent emission. The disadvantage of reactive adhesivesof the second type is that they generally contain physiologicallyhazardous isocyanates, epoxides, polyamines and polyamides.Understandably, users often have reservations about handling suchisocyanates, epoxides, polyamines and polyamides.

Accordingly, there was a need for water-based adhesives which could evenbe used under conditions where evaporation of the water is difficult orlargely impossible. There was also a need for water-based adhesiveswhich could even be used in conjunction with water-sensitive substrates.However, such adhesives would be expected to have an adequate pot life,to be able to withstand load stress very soon after the end of their potlife and, in addition, to be suitable for use even indoors, particularemphasis being placed on minimal odor emission. In addition, theadhesives would be expected to show sufficient resistance to water sothat they could be used in environments with high air humidity and thestrength of the bond would not be affected by at least brief contactwith water. Property profiles such as these are required, for example,for adhesives used for bonding laminate or parquet to correspondingsubstrates in interior rooms.

EP-A 0 782 977 relates to a preparation for waterproofing orvapor-proofing a substrate surface. The document in question describestwo components, one an aqueous latex of a natural or synthetic rubberand the other a dispersion of a vulcanizing agent and a hygroscopiccompound in an oil phase. Hydrocarbon oils are mentioned as a suitableoil phase, mixtures of hydrocarbon oils, for example a mixture ofaromatic and aliphatic compounds, being particularly preferred. It isalso stated in the cited document that synthetic liquid plasticizers,such as phthalates or adipates, may be present in the oil phase foradjusting the flow properties. The disadvantage of the system describedin the cited document is that both the binder in the aqueous oil phaseand the vulcanizing agent can lead to serious odor emissions. Inaddition, the described suspension of a hygroscopic compound in thehydrocarbon oils mentioned tends to undergo phase separation so that theuser has to carry out a dispersion step before using the describedpreparation. In addition, the described preparations can showunsatisfactory curing behavior for adhesive applications because arelatively long period elapses between the end of the pot life of thepreparation and the actual readiness of a surface coating formed fromthe described preparation to withstand load stress. Finally, nothing issaid in the cited document about the use of the compositions describedtherein as adhesives.

When adhesives are used for bonding floor coverings, effectiveinsulation of the floor covering from the substrate to which it isapplied is often required. This insulation relates on the one hand tothe transfer of heat between floor and floor covering and on the otherhand to the insulating properties of the floor covering, particularlywith respect to solid-borne sound. The adhesives known from the priorart are unsatisfactory in this regard because heat insulation andsolid-borne sound insulation or both cannot be achieved sufficiently, ifat all, using known adhesives.

SUMMARY OF THE INVENTION

Accordingly, the problem addressed by the invention was to providewater-based adhesives which could even be used under the conditionsmentioned above and which would not have any of the disadvantages of theprior art.

The problem stated above is solved by an adhesive system of at least twocomponents A and B, the adhesive system comprising an aqueous dispersionof a polyurethane or a polymer as component A and a dispersion of adrying agent in an oil phase with high polarity as component B.

DETAILED DESCRIPTION OF THE INVENTION

Accordingly, the present invention relates to an adhesive system of atleast two separate components A and B, characterized in that itcomprises

-   a) as component A an aqueous dispersion of a polymer obtainable by    polyaddition or by polymerization of a monomer containing at least    one olefinically unsaturated double bond or a mixture of two or more    such monomers or an aqueous dispersion of a mixture of two or more    such polymers (polymer dispersion) and-   b) as component B a dispersion of a drying agent in an oil phase    liquid at 23° C., the oil phase containing at least 0.1% by weight    of a compound liquid at 23° C. which is soluble in the oil phase and    which contains at least one covalent single, double or triple bond    between a carbon atom and a hetero atom or a mixture of two or more    such compounds.

An “adhesive system” in the context of the present invention isunderstood to be a system of which the separate components are mixed bythe user before bonding to form the composition actually working as anadhesive in the sense of the present invention. In the context of thepresent invention, an adhesive system according to the inventioncomprises at least two separate components A and B.

However, an adhesive system according to the invention may equally wellcomprise more than two components, for example three, four or five ormore components. The components present in the adhesive system accordingto the invention may be present in individual containers designed forseparate handling, the actual adhesive being prepared by combining andmixing the contents of the separate containers.

However, the present invention also encompasses adhesive systems wherethe individual components, although physically separated from oneanother, are accommodated in a single container. Systems such as theseare, for example, cartridge systems with two or more compartments. Insuch systems, one or more compartments may each hold one component andone or more other compartments may each hold another component. Toprepare the adhesive from the individual components of the adhesivesystem, the corresponding compartments are simultaneously emptied andthe contents are mixed to form the adhesive, for example in a staticmixer, before application to the actual substrate. The adhesive systemaccording to the invention also encompasses systems where the componentsforming the adhesive are present in separate compartments in acontainer, the compartments being joined, for example, by destruction ofthe partitions between them by external pressure and their contentsbeing subsequently mixed, for example, by tumbling of the container.

In addition, “adhesive systems” in the context of the present inventionare systems where components A and B are present, for example, on thelines of a one-component system, but are separated from one another byencapsulation of one of the components, more particularly byencapsulation of component B. Known microencapsulation techniques, forexample spray drying and other techniques known to the expert, may beused for this purpose.

According to the invention, component A is an aqueous dispersion of apolymer obtainable by polymerization of a monomer containing at leastone olefinically unsaturated double bond or a mixture of two or moresuch monomers or an aqueous dispersion of a mixture of two or more suchpolymers. Aqueous dispersions such as these are also referred to hereinas polymer dispersions. Polymer dispersions obtainable by dispersion ofa polymer present, for example, in powder form or of a mixture of two ormore such polymers in water are suitable for use as component A.However, a preferred embodiment of the present invention ischaracterized by the use of aqueous dispersions which are the outcome ofsuspension or emulsion polymerization. According to the invention,however, other polymers—either in the form of aqueous dispersions orpowders—may be added to such polymer dispersions. Dispersions suitableas component A may be prepared by standard processes for preparingpolymer dispersions, such processes being known to the expert.

The polymer dispersions suitable for use as component A in accordancewith the invention may be prepared, for example, from monomerscontaining at least one olefinically unsaturated double bond(olefinically unsaturated monomers) which are accessible to suspensionor emulsion polymerization. Polymers suitable for the preparation of theaqueous dispersions usable as component A are, for example, vinyl esterpolymers of which the monomeric basic unit is a vinyl ester of a linearor branched carboxylic acid containing about 2 to about 44, for exampleabout 3 to about 15 carbon atoms. Suitable monomers for thesehomopolymeric or copolymeric polyvinyl esters are vinyl formate, vinylacetate, vinyl propionate, vinyl isobutyrate, vinyl pivalate,vinyl-2-ethylhexanoate, vinyl esters of saturated branchedmonocarboxylic acids containing 9 to about 15 carbon atoms in the acidcomponent, vinyl esters of relatively long-chain, saturated orunsaturated fatty acids, such as vinyl laurate, vinyl stearate or vinylesters of benzoic acid and substituted derivatives of benzoic acid, suchas vinyl-p-tert.butyl benzoate. The vinyl esters mentioned may bepresent in the polyvinyl ester either individually or in the form ofmixtures of two or more of the vinyl esters mentioned. In a preferredembodiment of the invention, the percentage content of these vinylesters in the polymer present in the aqueous dispersion used ascomponent A as a whole is at least about 50% by weight, for example atleast about 75% by weight. In another preferred embodiment of thepresent invention, vinyl acetate is used as the olefinically unsaturatedmonomer.

In another preferred embodiment of the present invention, the polymerdispersion may also contain polymers which, besides one of theabove-mentioned vinyl esters or a mixture of two or more thereof, mayalso contain other comonomers. Other ethylenically unsaturated monomerswhich may be copolymerized with the above-mentioned vinyl esters are,for example, acrylic acid, methacrylic acid and esters thereof withprimary or secondary, saturated monohydric alcohols containing 1 toabout 28 carbon atoms, such as methanol, ethanol, propanol, butanol,2-ethylhexyl alcohol, cycloaliphatic alcohols, such as cyclohexanol,hydroxymethyl cyclohexane or hydroxyethyl cyclohexane. Also suitable arethe esters of the above-mentioned ethylenically unsaturated acids withrelatively long-chain fatty alcohols. Other suitable comonomers areethylenically unsaturated dicarboxylic acids, such as maleic acid,fumaric acid, itaconic acid or citraconic acid and mono- or diestersthereof with saturated monohydric aliphatic alcohols containing 1 toabout 28 carbon atoms. The percentage content of such comonomers in thepolymers present in the polymer dispersion may be up to about 25% byweight, for example about 0.1 to about 15% by weight.

Other suitable comonomers are simple, ethylenically unsaturatedhydrocarbons, such as ethylene or α-olefins containing about 3 to about28 carbon atoms, for example propylene, butylene, styrene, vinyltoluene, vinyl xylene and halogenated unsaturated aliphatichydrocarbons, such as vinyl chloride, vinyl fluoride, vinylidenechloride, vinylidene fluoride and the like. The percentage content ofthese comonomers in the polymers used in the polymer dispersions may beup to about 50% by weight or less, for example about 0.5 to about 25% byweight.

Polyethylenically unsaturated monomers, for example, are also suitableas comonomers. Examples of such monomers are butadiene, diallylphthalates, diallyl maleate, triallyl cyanurate, tetraallyloxyethane,divinylbenzene, butane-1,4-diol dimethacrylate, triethylene glycoldimethacrylate, divinyl adipate, allyl acrylate, allyl methacrylate,vinyl crotonate, methylene bis-acrylamide, hexanediol diacrylate,pentaerythritol diacrylate or trimethylolpropane triacrylate or mixturesof two or more thereof. The percentage content of these comonomers inthe polymers prepared by emulsion polymerization present in the polymerdispersions is up to about 10% by weight, for example about 0.01 toabout 5% by weight.

Other suitable comonomers are ethylenically unsaturated compoundscontaining N-functional groups. Such compounds include, for example,acrylamide, methacrylamide, allyl carbamate, acrylonitrile, N-methylolacrylamide, N-methylol methacrylamide, N-methylol allyl carbamate andthe N-methylol esters, alkylethers or Mannich bases of N-methylolacrylamide or N-methylol methacrylamide or N-methylol allyl carbamate,acrylamidoglycolic acid, acrylamidomethoxyacetic acid methyl ester,N-(2,2-dimethoxy-1-hydroxyethyl)acrylamide, N-dimethylaminopropylacrylamide, N-dimethylaminopropyl methacrylamide, N-methyl acrylamide,N-methyl methacrylamide, N-butyl acrylamide, N-butyl methacrylamide,N-cyclohexyl acrylamide, N-cyclohexyl methacrylamide, N-dodecylacrylamide, N-dodecyl methacrylamide, ethyl imidazolidone methacrylate,N-vinyl formamide, N-vinyl pyrrolidone and the like.

Other polymer dispersions suitable for use as component A in accordancewith the invention contain polymers or copolymers of styrene or one ofits derivatives, for example α-methylstyrene. Suitable polymers have astyrene content of more than 30% by weight, for example more than 50% byweight or more than 80% by weight of the total monomeric units presentin the polymer. Suitable comonomers are, for example, acrylates andmethacrylates containing 1 to about 12 carbon atoms in the alcoholcomponent, for example 2 to about 8 carbon atoms. Other suitablecomonomers which may be present in a corresponding styrene copolymereither individually or in the form of a mixture of two or more thereofare, for example, vinyl esters, maleic acid esters, ethylene,acrylamide, acrylic acid, butadiene or acrylonitrile.

Other organic polymers suitable in accordance with the invention for theproduction of the polymer dispersions according to the invention belongto the group of styrene/butadiene rubbers (SBRs). Such rubbers areproduced by copolymerization of styrene and butadiene and generallycontain the two monomers in a ratio by weight of about 23.5:76.5 orabout 40:60. The SBRs are normally produced by emulsion polymerizationin water.

Another group of suitable polymers are the polyethylene homopolymers andcopolymers. A radical polymerization of ethylene is carried out, forexample, by high-pressure polymerization to LDPE under pressures ofabout 1,400 to 3,500 bar and at temperatures of 150 to 350° C. Thereaction is initiated by oxygen or peroxides. Suitable comonomers arelinear or branched α,β-unsaturated olefins.

Another group of suitable polymers are the polyacrylates or thepolymethacrylates or copolymers of polyacrylates and polymethacrylates.The polymers mentioned may optionally contain small amounts (up to about10%) of free acrylic or methacrylic acid groups.

Also suitable as polymers in component A are the polyurethanesobtainable by polyaddition of polyisocyanates containing correspondinggroups with a functionality of at least two to isocyanate groups.

Polyurethanes are obtainable, for example, by reacting

-   i) polyisocyanates with-   ii) polyols and-   iii) optionally compounds containing primary and/or secondary amino    groups and optionally other functional groups which have a    functionality of one or more to isocyanates and-   iv) optionally compounds containing at least one isocyanate-reactive    group and at least one group ionizable by addition of a base or an    acid or by quaternization.

Suitable polyurethanes may be dispersible, for example, in the presenceof an emulsifier although they may also be substantiallyself-dispersible in water.

In the context of the invention, “polyurethanes substantiallyself-dispersible in water” are understood to be polyurethanes which canbe dispersed in water by addition of only small quantities of dispersionaids or even without the addition of any dispersion aids at all.Polyurethanes such as these require at most an addition of dispersionaids of about 5% by weight, preferably less than 3% by weight and morepreferably less than 1% by weight, based on dispersion dry weight and,more particularly, based on the weight of the binders in the dispersion.

Binders or polymeric binders in the context of the invention areunderstood to be those polymeric constituents of the polyurethanes whichare involved in the formation of the dry coating or bond and whichprovide the coating or bond with mechanical stability.

Organic solvents with a boiling point above 100° C. (for exampleN,N-dimethyl formamide (DMF), N,N-dimethylacetamide (DMAc) orN-methylpyrrolidone (NMP) may be present in the polyurethane dispersionsin small quantities, for example in a quantity of at most about 15% byweight, preferably in a quantity of less than 10% by weight and morepreferably in a quantity of less than 8% by weight, based on thedispersion as a whole.

The polyisocyanates typically used in polyurethane chemistry may be usedas component i) for the production of the polyurethanes according to theinvention.

Particularly suitable polyisocyanates are diisocyanates X(NCO)₂, where Xis an aliphatic hydrocarbon radical containing 4 to 12 carbon atoms, acycloaliphatic or aromatic hydrocarbon radical containing 6 to 15 carbonatoms or an araliphatic hydrocarbon radical containing 7 to 15 carbonatoms. Examples of such diisocyanates are tetramethylene diisocyanate,hexamethylene diisocyanate, dodecamethylene diisocyanate,1,4-diisocyanatocyclohexane,1-isocyanato-3,3,5-trimethyl-5-isocyanatomethyl cyclohexane (IPDI),2,2-bis-(4-isocyanatocyclohexyl)-propane, trimethylhexane diisocyanate,1,4-diisocyanatobenzene, 2,4-diisocyanatotoluene,2,6-diisocyanatotoluene, 4,4′-diisocyanatodiphenyl methane, tetramethylxylylene diisocyanate (TMXDI), 2,4′-diisocyanatodiphenyl methane,p-xylylene diisocyanate, the somers ofbis-(4-isocyanatocyclohexyl)-methane, such as the trans/trans, thecis/cis and the cis/trans isomer, and mixtures of these compounds.

Suitable mixtures of these isocyanates are, in particular, mixtures ofthe respective structural isomers of diisocyanatotoluene anddiisocyanatodiphenylmethane, more especially the mixture of 80 mol-%2,4-diisocyanatotoluene and 20 mol-% 2,6-diisocyanatotoluene. Mixturesof aromatic isocyanates, such as 2,4-diisocyanatotoluene and/or2,6-diisocyanatotoluene, with aliphatic or cycloaliphatic isocyanates,such as hexamethylene diisocyanate or IPDI, are also particularlyadvantageous, the preferred mixing ratio of aliphatic to aromaticisocyanates being about 4:1 to 1:4.

In order to produce polyurethanes with a certain degree of branching orcrosslinking, trifunctional and/or tetrafunctional isocyanates, forexample, may be used. Such isocyanates are obtained, for example, byreacting difunctional isocyanates with one another in such a way thattheir isocyanate groups are partly derivatized to allophanate, biuret orisocyanurate groups. Commercially available compounds are, for example,the isocyanurate or the biuret of hexamethylene diisocyanate.

Other suitable polyisocyanates of relatively high functionality are, forexample urethane polyisocyanates based on 2,4- and/or2,6-diisocyanatotoluene, IPDI or tetramethylene diisocyanate on the onehand and low molecular weight polyhydroxy compounds, such as trimethylolpropane, on the other hand.

For good film formation and elasticity, component ii) may be selected,for example, from relatively high molecular weight polyols, preferablydiols, with a molecular weight of, for example, about 500 to 5,000 orabout 1,000 to about 3,000 g/mol.

The polyols of component ii) are, for example, polyesterpolyols whichare known, for example, from Ullmanns Enzyklopädie der technischenChemie, 4th Edition, Vol. 19, pp. 62-65. Preferred polyesterpolyols areobtained by reaction of dihydric alcohols with polybasic, preferablydibasic polycarboxylic acids. The polycarboxylic acids may be aliphatic,cycloaliphatic, araliphatic, aromatic or heterocyclic and may optionallybe substituted, for example by halogen atoms, and/or unsaturated.Examples of such polycarboxylic acids are suberic acid, azelaic acid,phthalic acid, isophthalic acid, phthalic anhydride, tetrahydrophthalicanhydride, hexahydrophthalic anhydride, tetrachlorophthalic anhydride,endomethylenetetrahydrophthalic anhydride, glutaric anhydride, maleicacid, maleic anhydride, fumaric acid and/or dimeric fatty acids. Thepolycarboxylic acids mentioned may be used either individually as soleacid component or in admixture with one another for the synthesis ofcomponent i). Preferred carboxylic acids correspond to the generalformula HOOC—(CH₂)_(y)—COOH, where y is a number of 1 to 20, preferablyan integer of 2 to 20, for example succinic acid, adipic acid,dodecanedicarboxylic acid and sebacic acid. Instead of the freepolycarboxylic acids, the corresponding polycarboxylic anhydrides orcorresponding polycarboxylic acid esters of lower alcohols or mixturesthereof may also be used for the production of the polyester polyols.

Suitable polyhydric alcohols for reaction with the polycarboxylic acidcomponent for the synthesis of component i) are, for example, ethyleneglycol, propane-1,2-diol, propane-1,3-diol, butane-1,3-diol,butene-1,4-diol, butine-1,4-diol, pentane-1,5-diol, hexane-1,6-diol,neopentyl glycol, bis-(hydroxymethyl)-cyclohexanes, such as1,4-bis-(hydroxymethyl)-cyclohexane, 2-methylpropane-1,3-diol, methylpentanediols, also diethylene glycol, triethylene glycol, tetraethyleneglycol, polyethylene glycol, dipropylene glycol, polypropylene glycols,dibutylene glycol and polybutylene glycol. Preferred polyhydric alcoholsare neopentyl glycol and alcohols with the general formulaHO—(CH₂)_(x)—OH, where x is a number of 1 to 20, preferably an integerof 2 to 20. Examples of such alcohols are ethylene glycol,butane-1,4-diol, hexane-1,6-diol, octane-1,8-diol and dodecane-1,12-diol.

Also suitable are polyetherdiols, preferably polyoxyethylene alcoholswith a molecular weight of at least about 150, preferably at least about200, which integrate hydrophilic sections into the polyester andoptionally provide for self-dispersibility of the polyester or thepolyurethane produced therefrom or at least facilitate dispersibility.

Also suitable as component ii) are polycarbonate diols which may beobtained, for example, by reacting phosgene with an excess of the lowmolecular weight alcohols mentioned as synthesis components for thepolyesterpolyols.

Lactone-based polyesterdiols are also suitable as component ii).Lactone-based polyesterdiols are homopolymers or copolymers of lactones,preferably hydroxyl-terminated products of the addition of lactones ontosuitable difunctional starter molecules. Examples of suitable lactonesare ε-caprolactone, β-propiolactone, γ-butyrolactone and/ormethyl-ε-caprolactone and mixtures thereof. Suitable starter componentsare, for example, the low molecular weight dihydric alcohols mentionedabove as synthesis component for the polyester polyols. Low molecularweight polyester diols or polyether diols may also be used as startersfor the production of the lactone polymers. Instead of the lactonepolymers, the corresponding chemically equivalent polycondensates of thehydroxy-carboxylic acids corresponding to the lactones may also be used.

The polyester polyols may also be synthesized with the assistance ofsmall quantities of monofunctional monomers and/or monomers of higherfunctionality.

In addition, polyether diols may be used as component ii). They may beobtained in particular by polymerization of ethylene oxide, propyleneoxide, butylene oxide, tetrahydrofuran, styrene oxide or epichlorohydrinon their own, for example in the presence of BF₃, or by addition ofthese compounds—optionally in admixture or successively—onto startercomponents containing reactive hydrogen atoms, such as water, alcoholsor amines, for example ethylene glycol, propane-1,2-diol,propane-1,3-diol, 1,2-bis-(4-hydroxydiphenyl)-propane or aniline.

Where suitable polyethers containing polyoxyethylene units with amolecular weight of at least about 150 and preferably of at least about200 are used for the production of the polyurethanes, it is possible toproduce polyurethanes self-dispersible in water which do not require theuse of other hydrophilic structural units in the polyurethane.

Alcohols with a functionality of more than two may be used in smallquantities both for the production of the polyester polyols and for theproduction of the polyether polyols. More particularly, compounds suchas these are, for example, trimethylolpropane, pentaerythritol,glycerol, sugars, such as glucose for example, oligomerized polyols suchas, for example, dimeric or trimeric ethers of trimethylolpropane,glycerol or pentaerythritol, partly esterified polyhydric alcohols ofthe above-described form, such as for example partly esterifiedtrimethylolpropane, partly esterified glycerol, partly esterifiedpentaerythritol, partly esterified polyglycerol and the like, monobasicaliphatic carboxylic acids preferably being used for esterification. Thehydroxyl groups of the polyols may optionally be etherified by reactionwith alkylene oxides. The above-mentioned compounds are also suitable asstarter components for the synthesis of the polyether polyols.

The polyol compounds with a functionality of >2 are preferably used inonly small quantities for the synthesis of the polyester polyols orpolyether polyols.

Polyhydroxyolefins, preferably those containing two terminal hydroxylgroups, for example α,ω-dihydroxypolybutadiene,α,ω-dihydroxypolymethacrylates or α,ω-dihydroxypolyacrylates, are alsosuitable for use as component ii).

The polyols listed above as suitable for use as component ii) may alsobe used in the form of mixtures in any ratios.

The hardness and the elasticity modulus of the polyurethanes may befurther increased by using other low molecular weight diols or polyolsas polyols.

The other polyols used are, above all, the above-mentioned short-chainalkanediols, preferably neopentyl glycol and the unbranched C₂₋₁₂ diols,such as for example ethylene glycol, butane-1,4-diol, pentane-1,5-diolor hexane-1,6-diol.

The components described for the production of the polyurethanedispersions may also be used in the form of mixtures for the purposes ofthe invention.

Component iii) may be selected, for example, from chain extenders ormore than difunctional compounds suitable for introducing branches whichcontain at least one primary or secondary amino group or—where more thanone amino group per molecule is present—both primary and secondary aminogroups.

Besides the amino groups, the compounds of component iii) may containother functional groups, more particularly isocyanate-reactive groups.These include, in particular, the hydroxyl group or the mercapto group.

The compounds suitable for use as component iii) in accordance with theinvention include, for example, monoaminoalcohols containing analiphatically bound hydroxyl group, such as ethanolamine,N-methylethanolamine, N-ethylethanolamine, N-butylethanolamine,N-cyclohexylethanolamine, N-tert.butyl ethanolamine, leucinol,isoleucinol, valinol, prolinol, hydroxyethyl aniline,2-(hydroxymethyl)-piperidine, 3-(hydroxymethyl)-piperidine,2-(2-hydroxyethyl)-piperidine, 2-amino-2-phenylethanol,2-amino-1-phenylethanol, ephedrine, p-hydroxyephedrine, norephedrine,adrenalin, noradrenalin, serine, isoserine, phenylserine,1,2-diphenyl-2-aminoethanol, 3-amino-1-propanol, 2-amino-1-propanol,2-amino-2-methyl-1-propanol, isopropanolamine, N-ethyl isopropanolamine,2-amino-3-phenylpropanol, 4-amino-1-butanol, 2-amino-1-butanol,2-aminoisobutanol, neopentanolamine, 2-amino-1-pentanol,5-amino-1-pentanol, 2-ethyl-2-butyl-5-aminopentanol, 6-amino-1-hexanol,2-amino-1-hexanol, 2-(2-aminoethoxy)-ethanol,3-(aminomethyl)-3,5,5-trimethyl cyclohexanol, 2-aminobenzyl alcohol,3-aminobenzyl alcohol, 3-amino-5-methyl benzyl alcohol, 2-amino-3-methylbenzyl alcohol.

If component iii) is to be used, for example, to produce chain branches,it is possible, for example, to use monoaminopolyols containing twoaliphatically bound hydroxyl groups, such as 1-aminopropane-2,3-diol,2-aminopropane-1,3-diol, 2-amino-2-methylpropane-1,3-diol,2-amino-2-ethylpropane-1,3-diol, 2-amino-1-phenylpropane-1,3-diol,diethanolamine, diisopropanolamine, 3-(2-hydroxyethylamino)-propanol andN-(3-hydroxypropyl)-3-hydroxy-2,2-dimethyl-1-amino groups.

Polyamines may also be used as component iii). Examples of suitablepolyamines include such compounds as hydrazine, ethylenediamine, 1,2-and 1,3-propylenediamine, butylenediamines, pentamethylenediamines,hexamethylenediamines such as, for example, 1,6-hexamethylenediamine,alkyl hexamethylenediamines such as, for example, 2,4-dimethylhexamethylenediamine, generally alkylenediamines containing up to about44 carbon atoms, including cyclic or polycyclic alkylenediamines whichmay be obtained, for example, from the dimerization products ofunsaturated fatty acids in known manner. Also usable, but not preferred,are aromatic diamines such as, for example, 1,2-phenylenediamine,1,3-phenylenediamine or 1,4-phenylenediamine. Higher amines such as, forexample, diethylenetriamine, aminomethyl diamino-1,8-octane andtriethylenetetramine may also be used in accordance with the invention.

Besides components i), ii) and iii), compounds containing at least oneisocyanate-reactive group and at least one group ionizable by additionof a base or an acid or by quaternization or a group already ionized bysuch a reaction may be used as component iv) in the production ofpolyurethanes. In the following text, the terms “anionic groups” and“cationic groups” are used synonymously both for the groups ionized byaddition of a base or an acid or by quaternization and for the freeacids or free bases unless otherwise stated.

The contribution of components containing anionic or cationic groups tothe total quantity of components is generally gauged so that the molarquantity of anionic or cationic groups, based on the quantity by weightof all the components used, is between 30 and 1,000, preferably between50 and 600 and more preferably between 80 and 500 mmol/kg.

Above all, compounds bearing anionic groups, such as compounds bearingsulfonate, carboxylate and phosphonate groups, are incorporated in thepolyurethane as component iv). The anionic groups are particularlysuitable either in the form of the free acid or preferably in the formof their alkali metal or ammonium groups, more particularly protonatedtertiary amino groups or quaternary ammonium groups.

Suitable monomers containing anionic groups are normally aliphatic,cycloaliphatic, araliphatic or aromatic carboxylic acids and sulfonicacids which carry at least one alcoholic hydroxyl group or at least oneprimary or secondary amino group. The hydroxyalkyl carboxylic acids,above all those containing 3 to 10 carbon atoms, are preferred.Dimethylolpropionic acid (DMPA) is particularly preferred.

Of particular practical importance as component iv) bearing cationicgroups are, above all, compounds containing tertiary amino groups, forexample tris-(hydroxyalkyl)-amines, N,N′-bis-(hydroxyalkyl)-alkylamines,N-hydroxyalkyl dialkylamines, tris-(aminoalkyl)-amines,N,N′-bis-(aminoalkyl)-alkylamines, N-aminoalkyl dialkylamines, the alkylgroups and alkanediyl units of these tertiary amines independently ofone another consisting of one to six carbon atoms. Also suitable arepolyethers containing tertiary nitrogen atoms and preferably twoterminal hydroxy groups which can be obtained in known manner, forexample by alkoxylation of amines containing two hydrogen atoms attachedto amine nitrogen, for example methylamine, aniline orN,N′-dimethylhydrazine. Polyethers such as these generally have amolecular weight of 500 to 6,000 g/mol.

These tertiary amines are converted into the ammonium salts either withacids, preferably strong mineral acids, such as phosphoric acid,sulfuric acid, hydrohalic acids, or with strong organic acids, such asformic acid or acetic acid for example, or by reaction with suitablequaternizing agents, such as C₁₋₆ alkyl halides, for example alkylbromides or chlorides.

According to the invention, the polymers mentioned may be present in thepolymer dispersion according to the invention both individually and inthe form of mixtures of two or more thereof.

In a preferred embodiment of the invention, a copolymer of vinyl acetateand ethylene (EVA copolymer) is used as the organic polymer. In anotherpreferred embodiment of the invention, the polymer dispersion containspolyvinyl acetate or polyacrylate, more especially polybutyl acrylate,or a mixture of polyvinyl acetate and polyacrylate.

In another preferred embodiment of the present invention, polymerdispersions containing at least one of the above-mentioned polymers witha molecular weight (M_(w)) of at least about 50,000 are used ascomponent A.

Dispersions suitable for the purposes of the invention contain, forexample, copolymers of vinyl acetate, ethylene and vinyl versatate.These copolymers are produced, for example, by copolymerization of about50 to about 75% by weight of vinyl acetate, about 5 to about 13% byweight of ethylene and about 5 to about 30% by weight of vinylversatate. Copolymers of styrene and butyl acrylate are also suitable.These copolymers are produced, for example, by copolymerization of about25 to about 75% by weight of styrene and about 25 to about 75% by weightof butyl acrylate. Other suitable copolymers are copolymers of styreneand butadiene. Copolymers such as these are produced, for example, bycopolymerization of about 25 to about 75% by weight of styrene and about25 to about 75% by weight of butadiene, copolymers with a glasstransition temperature T_(g) of at least about 15° C. or at least about20° C., for example at least about 25° C., being preferred. The solidscontents of the dispersions usable in accordance with the invention isfrom about 45 to about 70% by weight. The use of a dispersion of acopolymer of vinyl acetate, ethylene and vinyl versatate is particularlypreferred.

A polymer dispersion usable as component A contains the polymersmentioned in a quantity of at least about 30% by weight. In a preferredembodiment of the present invention, the percentage content of suchpolymers is at least about 45% by weight or at least about 50% byweight. However, the content of such polymers may also be higher, forexample at least about 55% by weight or at least about 65% by weight orhigher, for example at least about 70% by weight or at least about 75%by weight. In a particularly preferred embodiment of the presentinvention, the percentage content of the polymers mentioned is about 50to 70% by weight.

Besides the organic polymers obtainable by emulsion polymerizationmentioned thus far, a polymer dispersion suitable for use as component Ain accordance with the invention may also contain one or more additives.Suitable additives are, for example, protective colloids, antioxidants,pigments, fillers, plasticizers, preservatives, defoamers, film formingaids, perfumes, coupling agents, solvents, dyes, flameproofing agents,flow controllers, tackifiers, viscosity adjusters, dispersion aids,emulsifiers or thickeners or a mixture of two or more of the additivesmentioned.

Component A may contain, for example, a protective colloid or a mixtureof two or more protective colloids as additive. Suitable protectivecolloids are, for example, etherified cellulose derivatives, such ashydroxyethyl cellulose, hydroxypropyl cellulose or carboxymethylcellulose. Other suitable protective colloids are polyvinyl pyrrolidoneor polycarboxylic acids, such as polyacrylic acid or polymethacrylicacid, optionally in the form of their copolymers with optionallyOH-functional esters of acrylic or methacrylic acid, and copolymers ofmaleic acid or maleic anhydride with other ethylenically unsaturatedcompounds, such as methylvinylether or styrene. For example, polyvinylalcohol, more especially polyvinyl alcohol with a degree of hydrolysisof about 30 to about 100% by weight, for example about 60 to about 98%by weight or about 70 to about 88% by weight, or a mixture of two ormore such polyvinyl alcohols, may be used as the protective colloid. Asdescribed above, the protective colloids used in the polymer dispersionsusable as component A may be used individually. However, a mixture oftwo or more of the protective colloids mentioned may also be used inaccordance with the invention.

The total percentage content of the protective colloid(s) in the polymerdispersion used as component A is up to about 20% by weight, for exampleabout 0.1 to about 15 or about 1 to about 10% by weight.

Suitable antioxidants are, for example, phosphorous acid and saltsthereof, hypophosphorous acid and salts thereof, ascorbic acid andderivatives thereof (more particularly ascorbyl palmitate), tocopheroland derivatives thereof, mixtures of ascorbic acid derivatives andtocopherol derivatives, sterically hindered phenol derivatives, moreespecially BHA (tert.butylene-4-methoxyphenol) and BHT(2,6-di-tert.butylene-4-methylphenol), gallic acid and derivativesthereof, particularly alkyl gallates, aromatic amines, such asdiphenylamine, naphthylamine or 1,4-phenylenediamine, dihydroquinoline,organic sulfides and polysulfides, dithiocarbamates andmercaptobenzimidazole.

Suitable viscosity adjusters are, for example, cellulose ethers,hydrogenated castor oil, highly disperse silicas and ionic or nonionicthickeners, such as polyacrylic acid, or associative thickeners.

The plasticizers used are, for example, plasticizers based on phthalicacid, more particularly dialkyl phthalates, preferred plasticizers beingphthalic acid esters esterified with a linear alkanol containing about 6to about 12 carbon atoms.

Other suitable plasticizers are benzoate plasticizers, for examplesucrose benzoate, diethylene glycol dibenzoate and/or diethylene glycolbenzoate, where about 50 to 95% of all the hydroxyl groups have beenesterified, phosphate plasticizers, for example t-butylphenyl diphenylphosphate, polyethylene glycols and derivatives thereof, for examplediphenyl ethers of poly(ethyleneglycol), liquid resin derivatives, forexample the methyl ester of hydrogenated resin, vegetable and animaloils, for example glycerol esters of fatty acids and polymerizationproducts thereof.

The stabilizers or antioxidants usable as additives in accordance withthe invention include hindered phenols of high molecular weight (M_(n)),polyhydric phenols and sulfur- and phosphorus-containing phenols.Phenols suitable as additives for the purposes of the invention are, forexample,1,3,5-trimethyl-2,4,6-tris-(3,5-di-tert.butyl-4-hydroxybenzyl)-benzene;pentaerythritoltetrakis-3-(3,5-di-tert.butyl-4-hydroxyphenyl)-propionate;n-octadecyl-3,5-di-tert.butyl-4-hydroxyphenyl)-propionate;4,4-methylenebis-(2,6-di-tert.butylphenol);4,4-thiobis-(6-tert.butyl-o-cresol); 2,6-di-tert.butylphenol;6-(4-hydroxyphenoxy)-2,4-bis-(n-octylthio)-1,3,5-triazine;di-n-octadecyl-3,5-di-tert.butyl-4-hydroxybenzyl phosphonates;2-(n-octylthio)-ethyl-3,5-di-tert.butyl-4-hydroxybenzoate and sorbitolhexa-[3-(3,5-ditert.butyl-4-hydroxyphenyl)-propionate].

Suitable photostabilizers are, for example, those which are commerciallyobtainable as Tinuvin® (manufacturer: Ciba Geigy).

Suitable fillers or pigments are, for example, chalk, heavy spar,kaolin, carbon black, gypsum, Aerosil, silica gel, graphite, metaloxides of aluminium, iron, zinc, titanium, chromium, cobalt, nickel,manganese and the like. Also suitable are the mixed oxides, chromates,molybdates, carbonates, silicates, aluminates and sulfates of theabove-mentioned elements. Other suitable fillers are native or syntheticfibers, cellulose, wood chips, phthalocyanines or silica flour. Thefillers and pigments mentioned may be used individually or in the formof a mixture of two or more thereof.

The adhesive system according to the invention contains as component B adispersion of a drying agent in an oil phase liquid at 23° C., the oilphase containing at least 0.1% by weight of a compound liquid at 23° C.which is soluble in the oil phase and which contains at least onecovalent single, double or triple bond between a carbon atom and ahetero atom or a mixture of two or more such compounds.

In the context of the invention, the term “oil phase” encompasses acontinuous phase of one or more compounds liquid at 23° C. which areimmiscible or substantially immiscible with water. Poor miscibility withwater is present when a mixture of water and the corresponding oil phaseundergoes phase separation, the separate phases each containing smallquantities of the compound representing the other phase or thecorresponding mixture of two or more such compounds in dissolved form.In a preferred embodiment of the present invention, an “oil phase” onlycontains compounds which have a solubility in water at 23° C. of lessthan 1 g/l.

According to the present invention, the oil phase of the dispersion usedas component B contains a compound which has at least one covalentsingle, double or triple bond between a carbon atom and a hetero atom.The term “hetero atom” as used in the present text encompasses any atomswhich are capable of entering into a covalent single, double or triplebond with a carbon apart from hydrogen and carbon itself. In a preferredembodiment of the present invention, O, N, S and P in particular aretermed hetero atoms. Such compounds are also referred to as polarcompounds in the present text.

In a preferred embodiment of the invention, the oil phase contains polarcompounds of which the polarity exceeds the polarity of normalhydrocarbon oils, for example paraffin oil or oils based on aromatichydrocarbons or mixtures thereof. The term “polarity” relates to thepolarity of the entire oil phase. If the oil phase only consists of asingle compound, the polarity of the oil phase corresponds to thepolarity of the corresponding compound. If the oil phase contains two ormore compounds which are liquid at a temperature of 23° C., the polarityof the oil phase as defined for the purposes of the present inventioncorresponds to the weighted average of the particular compounds formingthe oil phase.

In another preferred embodiment of the present invention, the oil phasecontains at least one polar compound which has one carbonyl group or twoor more carbonyl groups, one ester group or two or more ester groups orone ether group or two or more ether groups or one OH group or two ormore OH groups or a mixture of two or more of the groups mentioned.

In another preferred embodiment of the present invention, the oil phasecontains a compound with at least two ester groups or at least two ethergroups or at least one ester group and at least one ether group or atleast two ester groups and one ether group or at least two ether groupsand one ester group or at least three ester groups as the polarcompound.

In another preferred embodiment of the present invention, the percentagecontent of the polar compound or the mixture of two or more polarcompounds in the oil phase as a whole is at least about 30% by weight,for example at least about 50% weight, at least about 70% by weight orat least about 90% by weight. In another embodiment of the invention,the oil phase consists essentially of a polar compound or a mixture oftwo or more polar compounds corresponding to the above definition.

Any compounds immiscible or substantially immiscible with water aresuitable as the oil phase or as a constituent of the oil phase. Suitablecompounds are, for example, hydrocarbon oils, such as paraffin oils oraromatic hydrocarbon oils or mixtures thereof. Natural oils or fats ormixtures are also suitable as the oil phase or at least as a constituentof the oil phase, providing the corresponding compounds or mixtures areliquid at 23° C. Fatty compounds are also suitable.

“Fatty compounds” in the context of the invention include fatty acids,fatty alcohols and derivatives thereof providing they contain at leastone of the functional groups mentioned above. Their molecular weight isgenerally above 100 and, more particularly, above 200. The upper limitis 20,000 and preferably between 300 and 1,500. The percentage by weightof the polyether in the reaction product of ethylene oxide or propyleneoxide with the fatty compound is 1:0.01 to 3 and preferably 1:0.1 to 2.

“Fatty acids” in the context of the invention are understood to be acidswhich contain one or more carboxyl groups (—COOH). The carboxyl groupsmay be attached to saturated, unsaturated, unbranched or branched alkylgroups containing more than 8 and, in particular, more than 12 carbonatoms. Besides the —OH, —SH, —C═C—, —COOH, amino, anhydride or epoxidegroups mentioned above, they may contain other groups, such as ether,ester, halogen, amide, amino, urethane and urea groups. However,carboxylic acids, such as native fatty acids or fatty acid mixtures,dimer fatty acids and trimer fatty acids, are preferred. Actual examplesof the fatty acids besides the saturated fatty acids are, in particular,the monounsaturated or polyunsaturated acids palmitoleic acid, oleicacid, elaidic acid, petroselic acid, erucic acid, ricinoleic acid,hydroxymethoxy-stearic acid, 12-hydroxystearic acid, linoleic acid,linolenic acid and gadoleic acid.

Polyhydroxyfatty acids may also be used in addition to the naturallyoccurring fatty acids. They may be obtained, for example, by epoxidationof unsaturated fats and oils or esters of fatty acids with alcohols,ring opening with H-active compounds, for example alcohols, amines andcarboxylic acids, and subsequent saponification. The fats and oilsrequired as starting material may be both of vegetable origin and ofanimal origin or may optionally be synthesized by petrochemical methods.

The fatty acids may also be derived from oil- and fat-based rawmaterials obtainable, for example, by ene reactions, Diels-Alderreactions, transesterification reactions, condensation reactions,grafting reactions (for example with maleic anhydride or acrylic acidetc.) and epoxidation reactions. Examples of such raw materials are a)epoxides of unsaturated fatty acids, such as palmitoleic acid, oleicacid, elaidic acid, petroselic acid, erucic acid, linoleic acid,linolenic acid, gadoleic acid, b) reaction products of unsaturated fattyacids with maleic acid, maleic anhydride, methacrylic acid or acrylicacid, c) condensation products of hydroxycarboxylic acids, such asricinoleic acid or 12-hydroxystearic acid, and polyhydroxycarboxylicacids.

Not all the fatty acids described above are stable at room temperature.If necessary, therefore, derivatives of the above-mentioned fatty acids,such as esters or amides, may be used in accordance with the invention.

A preferred embodiment of the invention is characterized by the use ofesters or partial esters of the above-mentioned fatty acids withmonohydric or polyhydric alcohols. “Alcohols” in the context of theinvention are understood to be hydroxyl derivatives of aliphatic andalicyclic saturated, unsaturated, unbranched or branched hydrocarbons.Besides monohydric alcohols, these alcohols also include the lowmolecular weight hydroxyl-containing chain extending or crosslinkingagents known per se from polyurethane chemistry. Specific examples fromthe low molecular weight range are methanol, ethanol, propanol, butanol,pentanol, decanol, octadecanol, 2-ethylhexanol, 2-octanol, ethyleneglycol, propylene glycol, trimethylene glycol, tetramethylene glycol,2,3-butylene glycol, hexamethylene diol, octamethylene diol, neopentylglycol, 1,4-bis-hydroxymethyl cyclohexane, Guerbet alcohol,2-methylpropane-1,3-diol, hexane-1,2,6-triol, glycerol, trimethylolpropane, trimethylol ethane, pentaerythritol, sorbitol, formitol, methylglycoside, butylene glycol, dimer and trimer fatty acids reduced toalcohols. Alcohols derived from rosins, such as abietyl alcohol, mayalso be used for the esterification reaction.

The alcohols may even be replaced by OH-containing tertiary amines,polyglycerol or partly hydrolyzed polyvinyl esters.

In addition, polycarboxylic acids or hydroxycarboxylic acids may beadded for the oligomerization reaction. Examples of such acids areoxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid,glutaric acid, adipic acid, suberic acid, sebacic acid,1,11-undecanedioic acid, 1,12-dodecanedioic acid, phthalic acid,isophthalic acid, terephthalic acid, hexahydrophthalic acid,tetrahydrophthalic acid or dimer fatty acid, trimer fatty acid, citricacid, lactic acid, tartaric acid, ricinoleic acid, 12-hydroxystearicacid. Adipic acid is preferably used.

Besides the partly saponified fats, such as glycerol monostearate,examples of suitable esters are—preferably—the natural fats and oils ofnew rape, sunflowers, soya, flax, castor beans, coconuts, oil palms, oilpalm kernels and olive trees and methyl esters thereof. Preferred fatsand oils are, for example, beef tallow with a chain distribution of 67%oleic acid, 2% stearic acid, 1% heptadecanoic acid, 10% saturatedC₁₂-C₁₆ acids, 12% linoleic acid and 2% saturated acids containing morethan 18 carbon atoms or, for example, the oil of new sunflowers (NSf)with a composition of about 80% oleic acid, 5% stearic acid, 8% linoleicacid and about 7% palmitic acid. The corresponding epoxides and reactionproducts with maleic anhydride, for example, may of course also be used.Other examples are partly and completely dehydrated castor oil, partlyacetylated castor oil, ring opening products of epoxidized soybean oilwith dimer fatty acids.

Fatty acid esters and derivatives thereof obtainable by epoxidation mayalso be used. Examples of such esters include soya fatty acid methylester, linseed oil fatty acid methyl ester, ricinoleic acid methylester, epoxystearic acid methyl ester, epoxystearic acid-2-ethylhexylester. Preferred glycerides are the triglycerides, for example rapeseedoil, linseed oil, soybean oil, castor oil, partly and completelydehydrated castor oils, partly acetylated castor oil, soybean oilepoxide, linseed oil epoxide, rapeseed oil epoxide, epoxidized sunfloweroil.

In addition, the corresponding partial epoxides of the compoundsmentioned may also be used providing the partial epoxides at leastpredominantly still have at least one olefinically unsaturated doublebond.

In a preferred embodiment of the invention, an unsaturated fatty acidester or derivative obtainable by epoxidation or a mixture of two ormore such compounds is used as component A. Examples of such fatty acidsare soybean oil fatty acid methyl ester, linseed oil fatty acid methylester, ricinoleic acid methyl ester, epoxystearic acid methyl ester orepoxystearic acid-2-ethylhexyl ester.

Nucleophiles in the context of the present invention are understood tobe such alcohols as methanol, ethanol, ethylene glycol, glycerol ortrimethylol propane or amines such as, for example, ethanolamine,diethanolamine, triethanolamine, ethylenediamine or hexamethylenediamineor carboxylic acids such as acetic acid, the above-mentioned fattyacids, dimer fatty acid, maleic acid, fumaric acid or theabove-mentioned dibasic or polybasic, saturated or unsaturated di- andpolycarboxylic acids, phthalic acid or a mixture of two or more thereofor a mixture of two or more C₆₋₃₆ fatty acids. Examples of suchcompounds are ring opening products of epoxidized, unsaturated fattyacids or fats or oils, for example soybean oil, with carboxylic acids,for example with one or more of the above-mentioned fatty acids.

The fats and oils (triglycerides) may be used both in native form andafter thermal and/or oxidative treatment or in the form of thederivatives obtainable by epoxidation or by the addition of maleicanhydride or acrylic acid. Specific examples are palm oil, peanut oil,rapeseed oil, cottonseed oil, soybean oil, castor oil, partly andcompletely dehydrated castor oils, partly acetylated castor oils,sunflower oil, linseed oil, stand oils, blown oils, epoxidized linseedoil, rapeseed oil, coconut oil, palm kernel oil and tallows.

Other suitable derivatives are amides of the above-mentioned fattyacids. They may be obtained by reaction with primary and secondaryamines or polyamines, for example with monoethanolamine, diethanolamine,ethylenediamine, hexamethylenediamine, ammonia, but must still containnucleophilic groups for the reaction with the alkylene oxides.

“Fatty alcohols” in the context of the invention are understood to becompounds which contain one or more hydroxyl groups. The hydroxyl groupsmay be attached to saturated, unsaturated, unbranched or branched alkylgroups containing more than 8 carbon atoms and, in particular, more than12 carbon atoms. Besides the —SH, —C═C—, —COOH, amino, anhydride orepoxide groups required for the subsequent reaction with the alkyleneoxides, they may contain other groups, for example ether, ester,halogen, amide, amino, urea and urethane groups. Actual examples of thefatty alcohols according to the invention are ricinoleyl alcohol,12-hydroxystearyl alcohol, oleyl alcohol, erucyl alcohol, linoleylalcohol, linolenyl alcohol, arachidyl alcohol, gadoleyl alcohol, erucylalcohol, brassidyl alcohol, dimer diol (=hydrogenation product of dimerfatty acid methyl ester).

Symmetrical and non-symmetrical ethers and esters with mono- orpolycarboxylic acids may be used as derivatives of the fatty alcohols.Monocarboxylic acids are understood to include formic acid, acetic acid,propionic acid, butyric acid, valeric acid, caproic acid, oenanthicacid, caprylic acid, pelargonic acid, capric acid, undecanoic acid,lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid,palmitic acid, margaric acid, stearic acid, nonadecanoic acid, arachicacid, behenic acid, lignoceric acid, cerotic acid and melissic acid.Examples of polycarboxylic acids are oxalic acid, adipic acid, maleicacid, tartaric acid and citric acid. At the same time, the fatty acidsdescribed above, such as oleic acid oleyl ester for example, may also beused as the carboxylic acid.

The fatty alcohols may even be etherified, especially with polyhydricalcohols, for example alkyl polyglycosides and dimer diol ether.Mixtures of the above fatty compounds may of course also be used asstarter molecules for the reaction with the alkylene oxides.

Also suitable as the oil phase are the esters of aliphatic or aromaticcarboxylic acids, for example the esters of adipic acid, sebacic acid,citric acid, benzoic acid or the isomeric phthalic acids or mixturesthereof, providing the compounds or their mixtures are liquid at 23° C.Examples of such compounds are phthalic acid esters, adipic acid esters,sebacic acid esters or citric acid esters, polyester adipates, benzoicacid esters or rosin soft resin esters (liquid resins).

Hydrocarbon oils, such as paraffins, isoparaffins, aromatic andaliphatic oils and liquid hydrocarbon resins are also suitable as theoil phase.

The components B used in accordance with the invention in the adhesivesystems according to the invention contain a drying agent or a mixtureof two or more drying agents dispersed in the oil phase. According tothe invention, suitable drying agents are any compounds which eitherenter into a chemical reaction with water that is substantiallyirreversible under the conditions prevailing during the reaction orwhich adsorb the water so that it is only released slowly, if at all,under the conditions prevailing during the adsorption process. The twotypes of drying agent mentioned are normally referred to as chemicaldrying agents and as physical drying agents.

Drying agents suitable for use in component B in accordance with theinvention must enter into their reaction with water substantiallyirreversibly. “Irreversibly” in the context of the invention means thatthe chemical or physical reaction is substantially irreversible underthe conditions the adhesive system can expect to encounter in use. Suchconditions include, for example, a temperature range of about −30 toabout 120° C. and more particularly about 0 to about 100° C. or about 10to about 80° C. or about 20 to about 60° C. The reaction should also beirreversible under various air humidity conditions. Ideally, thechemical or physical reaction between water and the drying agent issubstantially irreversible over a range of 0 to 100% relative airhumidity.

Inorganic chemical drying agents include, in particular, drying agentswhich “set” with water (hydraulic binders). Hydraulic binders include,for example, the oxides of the alkali or alkaline earth metals, such asmagnesium oxide, barium oxide, calcium oxide, sodium oxide, lithiumoxide or potassium oxide. Other suitable hydraulic binders are cementswhich contain calcium silicates, calcium aluminates and calcium ferritesin varying composition. Suitable cements are, for example, blast furnacecement, trass cement, Portland oil shale cement, fly ash cement,phonolith cement, volcanic cement, sulfate slag cement, alumina cement,expanding cement or quick cement. Other suitable drying agents are theoxides of phosphorus and the polymeric phosphoric acids. Inorganicchemical drying agents also include compounds which react with waterwith incorporation of the water in their crystal lattice (formation ofwater of crystallization). Such compounds are, for example, magnesiumsulfate, sodium sulfate, copper sulfate, calcium sulfate, magnesiumcarbonate, calcium chloride, potassium carbonate, magnesium perchlorate,ettringite and the like.

Suitable physical drying agents are, in particular, physical inorganicdrying agents, for example zeolites, layered silicates, silica gels ormontmorillonites of the type normally used as molecular sieves.

The dispersion of a drying agent in an oil phase usable as component Bin accordance with the invention has a percentage drying agent content,based on component B as a whole, of at least about 0.1% by weight. Sincecomponents A and B are used by mixing to produce an adhesive, it isadvisable for both components to be adapted to one another in theiringredients and, preferably, to be delivered together as a kit.Accordingly, the drying agent content of component B should preferablybe gauged so that it is sufficient for drying component A, i.e. fortaking up at least a proportion of the water present in component Asufficient for drying. It is not absolutely essential in this connectionfor all the water to be removed from component A. It may be sufficientto remove only a certain percentage of the water, for example about 50%by weight, about 70% by weight or about 90% by weight. In a preferredembodiment of the present invention, however, the percentage content ofdrying agent in component B is gauged so that substantially all thewater in component A, i.e. at least about 95% by weight or at leastabout 99% by weight, can be bound. In a preferred embodiment of theinvention, therefore, component B contains the drying agent in aquantity of about 20 to about 90% by weight, for example in a quantityof about 30 to about 80% by weight or about 40 to about 70% by weight.Depending on the composition of component A, the content of drying agentin component B can be, for example, about 40 to about 60% by weight.

Suitable components B are, for example, mixtures of ettringite-formingcement in castor oil (mixing ratio 5:1 to 1:5), white lime in epoxidizedsoybean oil (mixing ratio 5:1 to 1:5) or Portland cement in a mixture ofdiethylene glycol dibenzoate, triethylene glycol dibenzoate anddipropylene glycol dibenzoate.

According to the invention, component B may contain another additive ora mixture of two or more other additives. Other additives are, forexample, protective colloids, antioxidants, pigments, fillers,preservatives, defoamers, film-forming aids, perfumes, coupling agents,solvents, dyes, flameproofing agents, flow controllers, tackifiers,viscosity and rheology adjusters, dispersion aids, emulsifiers,thickeners or antisedimenting agents.

In a preferred embodiment of the invention, the percentage content ofsuch additives in component B as a whole can be up to at most about 30%by weight but is preferably lower, for example about 0.5 to about 10% byweight.

The above-mentioned components A and B may be used for the production ofadhesives. Accordingly, the present invention also relates to a processfor the production of an adhesive in which at least two components A andB are mixed,

-   a) component A being an aqueous dispersion of a polymer obtainable    by polyaddition or by polymerization of a monomer containing at    least one olefinically unsaturated double bond or a mixture of two    or more such monomers or an aqueous dispersion of a mixture of two    or more such polymers and-   b) component B being a dispersion of a drying agent in an oil phase    liquid at 23° C., the oil phase containing at least 0.1% by weight    of a compound liquid at 23° C. which is soluble in the oil phase and    which contains at least one covalent single, double or triple bond    between a carbon atom and a hetero atom or a mixture of two or more    such compounds.

Besides components A and B, other components may optionally be used forthe production of the corresponding adhesive. These other components maybe, for example, organic or inorganic additives, such as sand, granularplastics, powdered plastics, granular rubbers, powdered rubbers, glassgranules or glass beads or a mixture of two or more of the additivesmentioned.

Accordingly, the present invention also relates to an adhesiveobtainable by mixing at least two components A and B,

-   a) component A being an aqueous dispersion of a polymer obtainable    by polyaddition or by polymerization of a monomer containing at    least one olefinically unsaturated double bond or a mixture of two    or more such monomers or an aqueous dispersion of a mixture of two    or more such polymers and-   b) component B being a dispersion of a drying agent in an oil phase    liquid at 23° C., the oil phase containing at least 0.1% by weight    of a compound liquid at 23° C. which is soluble in the oil phase and    which contains at least one covalent single, double or triple bond    between a carbon atom and a hetero atom or a mixture of two or more    such compounds.

It has been found that combinations of component A and component B mayalso be used as adhesives providing component B has only a smallcontent, if any, of polar compounds. Accordingly, the present inventionalso relates to the use of an adhesive system of at least two componentsA and B for the production of adhesives,

-   a) component A being an aqueous dispersion of a polymer obtainable    by polyaddition or by polymerization of a monomer containing at    least one olefinically unsaturated double bond or a mixture of two    or more such monomers or an aqueous dispersion of a mixture of two    or more such polymers and-   b) component B being a dispersion of a drying agent in an oil phase    liquid at 23° C.

In a preferred embodiment of the use according to the invention, the oilphase contains at least 0.1% by weight of a compound liquid at 23° C.which is soluble in the oil phase and which contains at least onecovalent single, double or triple bond between a carbon atom and ahetero atom or a mixture of two or more such compounds.

The adhesives obtainable by the process according to the invention aresuitable for bonding substrates of the same kind or of different kinds.Suitable substrates are, for example, wood, cork, metal, plastics,textiles, stone, concrete and the like. In a preferred embodiment of thepresent invention, the adhesives are used for bonding water-sensitivesubstrates, for example for bonding parquet or laminate to floors ininterior rooms.

Accordingly, the present invention also relates to the use of anadhesive according to the invention for bonding materials of wood, cork,metal, plastics, textiles, elastomers, stone or concrete.

The adhesives according to the invention are suitable both for bondingwater-permeable substrates and for bonding water-impermeable substrates.Thus, besides the above-mentioned materials, plastic substrates forexample, particularly in web or sheet form, for example elastomericplastics, may be bonded. The adhesives according to the invention areparticularly suitable for bonding elastomers to roofs or floors.

The invention is illustrated by the following Examples.

EXAMPLES

The following components A and B were used for the production ofadhesives:

Component A1: dispersion of 65% by weight vinyl acetate, 10% by weightethylene and 25% by weight vinyl versatate, solids content: ca. 60%Component A2: dispersion of 50% by weight styrene and 50% by weightbutyl acrylate, solids content: ca. 50% Component B1: ettringite-formingcement in castor oil (mixing ratio 2:1) Component B2: white lime inepoxidized soybean oil (mixing ratio 2:1)Practical Examples

The following different adhesives were prepared from the above-describedcomponents A and B by mixing the corresponding quantities and themixtures were evaluated:

Adhesive No. 1 2 3 4 Comp. A1 33 g 33 g 33 g Comp. A2 33 g Comp. B1 67 g67 g 67 g Comp. B2 67 g Rubber granules*  3 g Miscibility Good Good Verygood Very good Spreadability Good Satisfactory Good Very good (*Therubber granules were added to component B1 before mixing of the twocomponents)

Films were prepared from the adhesives and were evaluated on the basisof the following criteria:

Adhesive No. 1 2 3 4 Elasticity* (1-6) 2 5 3 5 Tack* (1-6) 3 6 2 6Hardness* (1-6) 3 2 3 4 Resilience* (1-6) 1 2 1 3 Exudation No No No No(*Scoring: 1 = very elastic, very tacky, very hard, high resilience 6 =inelastic, tack-free, soft, no resilience)

Commercial laminate was laid on cement screed slabs using the adhesives.Adhesion to the surface and to the substrate was good.

Insulating Properties of the Adhesive:

Test Arrangement:

Commercial laminate was laid on cement screed slabs:

-   a) loosely laid laminate on loose insulating layer of ethylene/vinyl    acetate granules on the screed slab (standard procedure in about 90%    of the laying of laminate)-   b) direct bonding to the screed slab with a non-elastic polyurethane    adhesive of the type typically used for bonding parquet and laminate    (in about 9% of laminate applications)-   c) bonding a solid-borne sound insulating layer (3 mm thick) of    ethylene/vinyl acetate granules with the above-mentioned adhesive    and then the laminate using the same adhesive (normal in about 1% of    the applications)-   d) direct bonding with the adhesive according to the invention    (adhesive No. 1 in the above Examples)    Results of Room Sound Measurements Using a Hammer for Sound    Generation:-   a) measurable sound level 93 db-   b) measurable sound level 89 db-   c) measurable sound level 83 db-   d) measurable sound level 83 db

Laying the laminate loosely on a sound-insulating layer (a) produces theworst results. Even simple bonding (b) with commercially availableproducts does not produce a clear advantage. Although bonding to thesound-insulating layer (c) has a good sound-insulating effect, it iscomplicated (2 steps) and expensive. Bonding with the adhesive (d)according to the invention produces a distinct gain in sound insulationand can be carried out in a single step. Accordingly, the adhesiveaccording to the invention is simple and inexpensive to apply to all,nowadays generally loosely laid hard floors (for example laminate,ready-made parquet).

1. An adhesive composition comprising at least two separate components Aand B, wherein: component A is an aqueous dispersion of a polymerobtainable by polyaddition or by polymerization of a monomer containingat least one olefinically unsaturated double bond or a mixture of two ormore such monomers or an aqueous dispersion of a mixture of two or moresuch polymers; and component B is a dispersion of a drying agent in anoil phase liquid at 23° C., the oil phase containing at least 0.1% byweight of a polar compound liquid at 23° C. which is soluble in the oilphase and which contains at least one covalent single, double or triplebond between a carbon atom and a hetero atom or a mixture of two or moresuch polar compounds.
 2. The adhesive composition of claim 1 wherein theoil phase contains at least 50% by weight of the polar compound or themixture of two or more polar compounds.
 3. The adhesive composition ofclaim 2 wherein the oil phase contains as the polar compound a compoundcontaining one carbonyl group or two or more carbonyl groups, one estergroup or two or more ester groups or one ether group or two or moreether groups or one OH group or two or more OH groups or a mixture oftwo or more of the foregoing groups.
 4. The adhesive composition ofclaim 1 wherein the oil phase contains as the polar compound a compoundcontaining at least two ester groups or at least two ether groups or atleast one ester group and at least one ether group or at least two estergroups and one ether group or at least two ether groups and one estergroup or at least three ester groups.
 5. The adhesive composition ofclaim 1 wherein the oil phase contains at least 90% by weight of a polarcompound or of a mixture of two or more polar compounds.
 6. The adhesivecomposition of claim 1 wherein component B contains at least 30% byweight of drying agent.
 7. The adhesive composition of claim 6 whereinthe drying agent is an inorganic drying agent.
 8. The adhesivecomposition of claim 1 wherein component A contains as the polymer apolymer obtainable by polymerization of acrylic acid or one or moreacrylic acid derivatives, methacrylic acid or one or more methacrylicacid derivatives, ethylene, vinyl acetate, styrene or one or morestyrene derivatives or by copolymerization of two or more of theforegoing compounds.
 9. A process for the production of an adhesivewhich contains at least two components A and B of claim 1 comprisingmixing the at least two components A and B.
 10. An adhesive obtained bythe process of claim
 9. 11. A method of using a dispersion of a dryingagent in an oil phase liquid at 23° C., the oil phase containing atleast 0.1% by weight of a polar compound liquid at 23° C. which issoluble in the oil phase and which contains at least one covalentsingle, double or triple bond between a carbon atom and a hetero atom ora mixture of two or more such compounds, for the production of anadhesive.
 12. A method of using the composition of claim 1 as anadhesive comprising applying the composition to a substrate.
 13. Themethod of claim 12 wherein the oil phase contains at least 0.1% byweight of a polar compound liquid at 23° C. which is soluble in the oilphase and which contains at least one covalent single, double or triplebond between a carbon atom and a hetero atom or a mixture of two or moresuch compounds.
 14. A method of using the adhesive composition of claim1 for bonding materials selected from the group consisting of wood,cork, metal, plastic, stone and concrete comprising applying theadhesive composition onto a surface of the material to be bonded.